Methylenedioxyphenyl compound as insecticide and pyrethrin synergist



. were, in and of themselves, insecticides.

Patented Oct. 26, 1948 v umrao STAT-ES PATENT OFFICE METHYLENEDIOXYPHENYL COMPOUND AS INSECTICIDE AND PYRETHRIN SYN ERGIST Oscar F. Hedenburg, Pittsburgh,-l'a., assignor, by

mesne assignments, to Harold W. Moburg, To-

ledo, Ohio No Drawing.

This invention relates to insecticides and synergists for insecticides and the preparation there were then tested, and it was found (Haller, La Forge, and Sullivan, Jour. Organic Chemistry, Mar. 1942;-VII, 183,185) that, while certain substances most closely related to sesamin (isosesamin and asarinin) were of like eifect, other substances, and particularly piperonal, safrol, and ethyl piperonylate, were ineffective.

I began in 1935 my investigation on insecticides of substances that contain the piperonyl group. In 1935 I made derivatives of safrol with cresols that contained the piperonyl group. These substances were tested, not for their synergistic effect when compounded with other toxic substances, but for-their effect, in and of themselves. They were tested by dissolving them in kerosene and evaluating them by the Feet-Grady method in their effect upon houseiiies, Musca domestz'cd. One of these substances, in a 1.40% solution, gave an 86% knockdown and a 50% kill-50%, that is to say,'

of the flies used in the test; another of .these substances that I then prepared, in a 1.25% solution, gave 69 knockdown and 24% kill. At that time i I was in search of compounds to take the place of pyrethrum; I was not in search of synergists; and my investigations showed that these safrol compounds (containing the piperonyl group) It was only at a subsequent time that (having preserved specimens, as I habitually do, of these first preparations) I tested them in combination with pyrethrum, and found them to have synergistic value.

In the Feet-Grady test the control is the-official test insecticide of the National Association of Insecticide and Disinfectant Manufacturers. It con- Application rebrumzr. 1943, Serial No. 477,444

8 Claims. (Cl. 167-33) In June, "1942, I formed a compound by the reaction at low temperature and in the presence tains about 100 mg. of pyrethrins 1 and 2 per 100 c. c. It is the standard used in the industry for making comparative tests. It is commonly spoken of, andI shall herein speak of it, as 0. T. I.

of sodium hydroxide as a catalyst of piperonal and methyl heptenone, according to the equation' Pipleronal (3,4 met ylene dloxy benzaldehyde) Methyl heptenone H o A} 0 (I? H H /CH1 cHr-o-c-co=c 3,4 methylene dioxy styryl isohexenyl ketone o ii iiils HIC & fi

This product I have designated No. 241. Tests upon it, as already described, gave the following Piperonal was reacted with' methyl 'isobutyl ketone at low temperature'and in the presence of sodium hydroxide, according to the equation- Piperonal Methyl isobutyl ketone H O (I? H /CH1 mo 1 CHT-C-r-CH O CH3 3,4 methylene dioxy styryl isobutyl ketone (piperonal methyl isobutyl ketone) This substance, identified as No. 242, under test,

gave the following results:

Ratio, kill Composition Knockdown Kill to knockdown , Per cent Per cent Per cent 17 No. 242 I. 50 mg. pyr. 1 and 2 6 7 73 0. T. I 96. 7 63.2

I reacted piperonal and methyl hexyl ketone at low temperature in the presence of sodium hydroxide, according to the equation' 3, 4 methylene dioxy styryl hexyl ketone (piper-owl methyl hexyl ketone) o as: chili-EH iii it This compound I designated N0. 267. Under test it showed- Ratio, kill Composition Knockdown Kill to knockdown V N 67 Per cent Per cent Per cent 0.5 o. 2 40 neg. pyr. l and 2 86 0. 'l. I 99. 7 66. 2 66 All of the products whose preparation and quality have been specified have a molecular weight of at least 190, and are responsive to the formula- H Ilii C") R-c=ccm in which R stands for piperonyl (methylene dioxy phenyl) R1 stands for hydrogen, and R2 stands for hydrogen, alkyl, aryl, aralkyl, or an alicyclic or heterocyclic group. And the same carbon ring may satisfy both of the terms R1 and R2, united to the several carbon atoms by different linkages.

Thus, in the foregoing formula, which represents the general formula for the type of compound forming the principal group of the compounds of the present invention, R specifically may be the piperonyl group, R1 may be hydrogen, and R2 may be a group consisting of hydrogen, alkyl, aryl, aralkyl, alicyclic, and an heterocyclic group, which groups may then be designated by R, the general formula noted above, then becomes I claim as my invention: 1. An insecticide and synergist for a pyrethrin insecticide having the general formula in which R is the 3,4-methylenedioxypheny1 radical and R2 is a substituent selected from the group consisting of the hydrogen atom and alkyl, aryl,

aralkyl, alicyclic and heterocyclic radicals.

2. An insecticide comprising a compound having the general formula in which R is the 3,4-methylenedioxyphenyl radical and R2 is a substituent selected from the group consisting of the hydrogen atom and alkyl, aryl, aralkyl, alic'yclic and heterocyclic radicals, the said compound having a molecular weight of at least 190, and a readily vaporizable vehicle therefor.

3. The compound having the structural formula i i i RC=OCR1 in which R is the 3,4-methylenedioxyphenyl radical and R2 is the n-hexyl radical.

4. An insecticide composition containing pyrethrins and as a synergist therefor a compound having the generic formula H i i R=G--CRs in which R is the 3,4-methylenedioxyphenyl radical and R2 is a substituent selected from the group consisting of the hydrogen atom and alkyl, aryl, aralkyl, alicyclic and heterocyclic radicals.

5. An insecticide composition containing pyrethrins and as a synergist therefor the compound of the formula H it R-7=CCR2 in which R is the 3,4-methylenedioxyphenyl radical and R2 is the n-hexyl radical.

6. An insecticide composition containing pyrethrins and as a synergist therefor the compound of the formula in which R is the 3,4-methylenedioxyphenyl radical and R2 is the n-hexyl radical, the pyrethrins and synergist compound being contained in a readily vaporizable liquid vehicle.

OSCAR F. HEDENBURG.

REFERENCES CITED The following references are of record in the file of thispatent:

UNITED STATES PATENTS Number Name Date 2,051,807 Allen Aug. 25, 1936 2,326,350 Gertler et al Aug. 10, 1943 OTHER REFERENCES Chem. Abst., vol. 25 (1931), page 5411, citing: Berichtewol. 64B, pages 1909-10 (1931).

Chem. Abst., vol. 19, page 467.

McIndoo, Dept. Bulletin No. 1201 (U. S. Dept. of Agriculture), published Mar. 19, 1924. 

